High Molecular Weight Polycyclic Aromatic Hydrocarbons Research Articles

Polycyclic aromatic hydrocarbons (PAHs) in blood serum of adults living in high and low-traffic volume areas in Malaysia: A comparative cross-sectional study

Ambient polycyclic aromatic hydrocarbons (PAHs) originate predominantly from fuel combustion of motor vehicles and have the potential to affect human health. However, there is insufficient knowledge regarding serum PAHs health risks among the Malaysian population. This study aims to compare PAH concentrations, distributions, correlations, and health risks in 202 blood serum samples drawn from residents living in high-traffic volume areas (Kuala Lumpur) and low-traffic volume areas (Hulu Langat) in Malaysia. Solid phase extraction and gas chromatography-mass spectrometry (GC-MS) were employed to extract and analyze blood serum samples. Questionnaires were distributed to obtain sociodemographic and contributing factors of serum PAHs. The mean total PAHs concentration in serum of the Kuala Lumpur group was 54.44 ng g−1 lipids, double the Hulu Langat group's concentration (25.7 ng g−1 lipids). Indeno(1,2,3-cd)pyrene (IcP) and acenaphthene (ACP) feature the most and least abundant compounds in both study groups. The mean concentrations of IcP and ACP in the Kuala Lumpur and Hulu Langat groups were 26.8 vs 12.68 and 0.27 vs 0.14 ng g−1 lipids, respectively. High-molecular-weight PAHs (HMW-PAHs) composed 85% of serum total PAHs in both groups. Significant correlations were found (i) between the individual serum PAH congeners (p < 0.01) and (ii) between serum PAHs and total lipids (p < 0.01). According to the questionnaire data, high traffic volume and outdoor hobbies were the only contributory factors that confirmed significant relationships with serum PAHs (p < 0.001). Health risk assessment was computed using benzo(a)pyrene (BaP) equivalent (BaPeq) and demonstrated that the Kuala Lumpur group has twofold greater carcinogenic risk than the Hulu Langat group (16.11 vs 7.76 ng g−1 lipids). Our study reveals that traffic volumes notably impact serum PAH levels and general health among the Malaysian population.

Assessing the Impact of Pre-Soaking to Enhance Laundering Efficacy of Firefighter Turnout Gear

Firefighters are exposed to hazardous chemicals at fire scenes, including polycyclic aromatic hydrocarbons (PAHs) among many others, which pose significant health risks. Current laundering practices are ineffective at removing persistent contaminants from turnout gear, necessitating further research to optimize cleaning methods. This study explores the impact of presoaking prior to the laundering process and the factors that can affect its effectiveness, including the presoaking duration and detergent concentration, in PAH removal when laundering. For this, contaminated fabric swatches were subjected to various presoaking durations (1, 3, and 12 h) and detergent concentrations (99:1 and 90:10 water-to-detergent ratios) before undergoing bench-scale washing. The cleaning efficacy was assessed for 16 PAH compounds, including both low-molecular-weight (LMW) PAHs and high-molecular-weight (HMW) PAHs. Moreover, the removal mechanisms of PAHs from turnout gear were fundamentally explained using partition coefficients and standard affinities with different parameters during washing. The results demonstrate that 3 h and 12 h of presoaking lead to 2.8 and 4.3 times greater HMW PAH removal, respectively. After 12 h of presoaking in a 90:10 water-to-detergent ratio, 97% of the LMW PAHs and 78% of the HMW PAHs were removed, compared to only an 11% removal of the HMW PAHs with a 99:1 ratio. Additionally, direct washing with a 90:10 ratio achieved comparable efficacy to that of presoaking with the same water-to-detergent ratio, indicating the crucial role of detergent concentration during laundering. These findings offer valuable insights for optimizing firefighter safety practices, emphasizing the role of presoaking and the appropriate methods to perform presoaking to mitigate firefighters’ occupational exposure risks to toxic substances and ensure gear reliability.

A case study on microlitter and chemical contaminants: Assessing biological effects in the southern coast of the Gulf of Finland (Baltic sea) using the mussel Mytilus trossulus as a bioindicator

Chemical and microlitter (ML) pollution in three Estonian coastal areas (Baltic Sea) was investigated using mussels (Mytilus trossulus). Polycyclic aromatic hydrocarbons (PAH) in mussel tissues were observed in moderate levels with high bioaccumulation factors for the more hydrophilic and low molecular weight PAH (LMW PAH), namely anthracene and fluorene. Tissue concentrations of polybrominated diphenyl ethers (PBDE) and cadmium within mussel populations exceeded the Good Environmental Status thresholds by more than 200% and 60%, respectively. Multiple contamination at the Muuga Harbour site by tributyltin, high molecular weight PAH, including the highly toxic benzo[c]fluorene and PBDE, coincided with the inhibition of acetylcholinesterase activity and a lower condition index of the mussels. The metabolization and removal of bioaccumulated LMW PAH, reflected in the dominance of oxy-PAH such as anthracene-9,10-dione, is likely associated with the increased activity of glutathione S-transferase in caged mussels. Only a few microplastic particles were observed among the ML in mussel tissues, with coloured cellulose-based microfibers being the most prevalent. The average concentration of ML in mussels was significantly higher at the harbour area than at other sites. The integrated biomarker response index values allowed for the differentiation of pollution levels across studied locations representing high, intermediate, and low pollution levels within the studied area.

Spatiotemporal distribution and inter-media transfer of polycyclic aromatic hydrocarbons in Shanghai, China: Historical patterns and future trends

Polycyclic Aromatic Hydrocarbons (PAHs) represent pervasive pollutants, posing health risks in urban environments. It is essential to comprehend the spatiotemporal distributions, composition profiles, and inter-media transfer processes of PAHs in various environmental compartments, influenced by both natural changes and anthropogenic activities. This study integrates historical and future spatiotemporally changing environmental parameters, including climate data, GDP, population data, land-use types, and hydrological variables, into the Multimedia Urban Model (MUM). This integration enables the simulation of spatiotemporal distributions and inter-media transfer fluxes of PAHs among six different media from the 2010s to the 2100s under two distinct Shared Socio-economic Pathways (SSP) scenarios in the megacity of Shanghai, China. The MUM model, featuring diverse gridded parameters, effectively captures PAH concentrations and movement across environmental compartments. Results indicate a decreasing trend in PAHs concentrations in the 2100s compared to the 2010s, with PAH concentrations in water, sediment, vegetation, and organic film covering impermeable surfaces under the SSP3–7.0 scenario higher than those of the SSP1–2.6 scenario. Low molecular weight PAHs dominate in the sediment, water, and air, whereas high molecular weight PAHs prevail in the organic film, vegetation, and soil. Sediment and soil serve as the predominant sinks for PAHs. The primary transport processes for PAH movement include air-film, air-soil, film-water, soil-air, and water-air. Almost all transfer fluxes exhibit a declining trend in future periods except for the air-film transport pathway. The principal input and removal routes for PAHs in Shanghai involve the advection of air and water. The study provides essential insights into the environmental behavior of PAHs and informs targeted pollution control in Shanghai. Additionally, it serves as a technical reference for similar pollution prediction research.

Particulate Matter (PM) and Parent, Nitrated and Oxygenated Polycyclic Aromatic Hydrocarbon (PAH) Emissions of Emulsified Heavy Fuel Oil in Marine Low-Speed Main Engine.

To understand the influences of emulsified fuel on ship exhaust emissions more comprehensively, the emissions of particulate matter (PM), nitrated, oxygenated and parent polycyclic aromatic hydrocarbons (PAHs) were studied on a ship main engine burning emulsified heavy fuel oil (EHFO) and heavy fuel oil (HFO) as a reference. The results demonstrate that EHFO (emulsified heavy fuel oil) exhibits notable abilities to significantly reduce emissions of particulate matter (PM) and low molecular weight PAHs (polycyclic aromatic hydrocarbons) in the gas phase, particularly showcasing maximum reductions of 13.99% and 40.5%, respectively. Nevertheless, burning EHFO could increase the emission of high molecular weight PAHs in fine particles and pose a consequent higher carcinogenic risk for individual particles. The total average (gaseous plus particulate) ΣBEQ of EHFO exhausts (41.5 μg/m3) was generally higher than that of HFO exhausts (18.7 μg/m3). Additionally, the combustion of EHFO (extra-heavy fuel oil) can significantly alter the emission quantity, composition, and particle-size distribution of PAH derivatives. These changes may be linked to molecular structures, such as zigzag configurations in C=O bonds. Our findings may favor the comprehensive environmental assessments on the onboard application of EHFO.

Source identification of polycyclic aromatic hydrocarbons (PAHs) in soils around crude oil contaminated area in Ohaji/Egbema, Imo State

ABSTRACT This study aims to determine the source of polycyclic aromatic hydrocarbons (PAHs) in the soils surrounding an area in Ohaji/Egbema, Imo State, that has been contaminated by crude oil. Soil samples were collected in the study area using a soil auger at a depth of 0–20 cm at three sampling locations (sample A, sample B, and sample C) in the Mmahu community in Ohaji/Egbema. In each of the sampling locations, twenty sub-samples were collected from twenty sampling points and pooled together to form representative samples for each of the sampling locations. Prior to GC-MS analysis, the composite samples were air-dried, sieved through a 2-mm mesh, and then kept in pet bottles that had been previously cleaned. The GC-MS investigations were carried out using a Shimadzu Model 2010 GC-MS (Shimadzu, Japan) fitted with an HP-5 MS fused silica column. This was used to quantify the 16 USEPA priority PAHs in the studied soils. The sum of the 16 USEPA priority PAHs in the sample locations ranged from 0.0192 mg/kg in the control sample to 10.73 mg/kg in sample A. Compared to high molecular weight PAHs (4–6 rings), the total concentration of low molecular weight PAHs (2–3 rings) was found to be substantially greater. According to the PAH molecular diagnostic ratio, all sampling points had low to high molecular mass ratios >1, which suggests that the origin of the PAH contamination was petrogenic. The petrogenic source of contamination was attributed to oil spillage around the study area. The knowledge of source identification of PAHs in soils helps in the determination of the most appropriate remediation strategy in order to prevent further contamination and minimise the risks to human health and the environment.

Contamination Levels and Accumulation Profiles of Polycyclic Aromatic Hydrocarbons (PAHs) in Surface Sediments from South Central Coast of Vietnam

Contamination Levels and Accumulation Profiles of Polycyclic Aromatic Hydrocarbons (PAHs) in Surface Sediments from South Central Coast of Vietnam

Fine-tuning an aromatic ring-hydroxylating oxygenase to degrade high molecular weight polycyclic aromatic hydrocarbon

Rieske nonheme iron aromatic ring-hydroxylating oxygenases (RHOs) play pivotal roles in determining the substrate preferences of polycyclic aromatic hydrocarbon (PAH) degraders. However, their potential to degrade high molecular weight PAHs (HMW-PAHs) has been relatively unexplored. NarA2B2 is an RHO derived from a thermophilic Hydrogenibacillus sp. strain N12. In this study, we have identified four “hotspot” residues (V236, Y300, W316, and L375) that may hinder the catalytic capacity of NarA2B2 when it comes to HMW-PAHs. By employing structure-guided rational enzyme engineering, we successfully modified NarA2B2, resulting in NarA2B2 variants capable of catalyzing the degradation of six different types of HMW-PAHs, including pyrene, fluoranthene, chrysene, benzo[a]anthracene, benzo[b]fluoranthene, and benzo[a]pyrene. Three representative variants, NarA2B2W316I, NarA2B2Y300F-W316I, and NarA2B2V236A-W316I-L375F, not only maintain their abilities to degrade low molecular weight PAHs (LMW-PAHs), but also exhibited 2-4 times higher degradation efficiency for HMW-PAHs in comparison to another isozyme, NarAaAb. Computational analysis of the NarA2B2 variants predict that these modifications altering the size and hydrophobicity of the active site pocket making it more suitable for HMW-PAHs. These findings provide a comprehensive understanding of the relationship between three-dimensional structure and functionality, thereby opening up possibilities for designing improved RHOs that can be more effectively used in the bioremediation of PAHs.

Evaluation of historical data on persistent organic pollutants and heavy metals in Lake Baikal: Implications for accumulation in marine environments

Lake Baikal, the largest freshwater lake by volume, provides drinking water and aquatic food supplies to over 2.5 million people. However, the lake has been contaminated with recalcitrant pollutants released from surrounding industrial complexes, agriculture, and natural lands, thereby increasing the risk of their bioaccumulation in fish and seals. Yet, a collective analysis of historical concentration data and their bioaccumulation potential as well as what factors drive their accumulation in fish or seals remains largely unknown. We analyzed concentration data from 42 studies collected between 1985 and 2019 in water, sediment, fish, and seals of Lake Baikal. Heavy metals had the highest concentrations in water and biota followed closely by polycyclic aromatic hydrocarbons (PAHs) and organochlorines. Among organochlorines, polychlorinated biphenyls (PCBs) showed the highest levels in water, surpassing hexachlorocyclohexane (HCH) concentrations, particularly after normalizing to solubility. While naphthalene and phenanthrene exhibited the highest average concentrations among polycyclic aromatic hydrocarbons (PAHs), their relative concentrations significantly decreased upon solubility normalization. The analysis confirmed that bioconcentration and biomagnification of organochlorine pesticides, PCBs, PAHs, and heavy metals depend primarily on source strength to drive their concentration in water and secondarily on their chemical characteristics as evidenced by the higher concentrations of low-solubility PCBs and high molecular weight PAHs in water and sediment. The differential biomagnification patterns of Cu, Hg, and Zn compared to Pb are attributed to their distinct sources and bioavailability, with Cu, Hg, and Zn showing more pronounced biomagnification due to prolonged industrial release, in contrast to the declining Pb levels. Dibenzo-p-dioxins were detected in sediment and seals, but not in water or fish compartments. These data highlight the importance of addressing even low concentrations of organic and inorganic pollutants and the need for more consistent and frequent monitoring to ensure the future usability of this and other similar essential natural resources.

Lagging pollution of polycyclic aromatic hydrocarbons in the rebuilt e-waste site: From the perspective of characteristics, sources, and risk assessment

Little information is known regarding how the lagged pollution of polycyclic aromatic hydrocarbon (PAH) influenced the environment and human health after an e-waste dismantling site was rebuilt. This study investigated the characteristics, sources, and risk assessment of PAHs in a rebuilt e-waste site and its surrounding farmland by analyzing the samples of soil, dust, water, and vegetable. Concentrations of PAHs in soil, vegetable and water in the rebuilt site were relatively higher than in its surrounding farmland. The concentrations in surface soils, soil columns, dust, vegetables, and water varied from 55.4 to 3990 ng g−1, 1.65 to 5060 ng g−1, 2190 to 2420 ng g−1, 2670 to 10,300 ng g−1, and 46.8 to 110 μg L−1 in the e-waste site, respectively. On the farmland, PAH concentrations in surface soils, vegetables, and water ranged from 41.5 to 2760 ng g−1, 506 to 7640 ng g−1, and 56.6 to 89.2 μg L−1, respectively. A higher proportion of high-molecular-weight PAHs (HMW-PAHs) appeared in all multimedia compared with low-molecular-weight PAHs (LMW-PAHs). Diagnostic ratio together with positive matrix factorization (PMF) revealed that vehicle emission was the primary source in this area, and the activity of e-waste disposal was another important source in the rebuilt e-waste site. Based on the deterministic health risks, people working in the reconstructed e-waste site were exposed to low risks, whereas the residents living near the surrounding farmland were exposed to low risk. Sensitivity analyses indicated that exposure frequency and PAH concentrations were the main factors that influenced exposure risk. This study provides valuable insight into the comprehension of the lagging pollution effects of PAH on the environment and human health after the e-waste site was rebuilt.

Seasonal variation and concentration of PAHs in Lake Balaton sediment: A study on molecular weight distribution and sources of pollution

The temporal and spatial variations of 16 Polycyclic Aromatic Hydrocarbons (PAHs) were examined at multiple sites around Lake Balaton from February 2023 to January 2024. The results indicated that the concentrations of PAHs in sediment were high during the winter months, 448.35 to 619.77 ng/g dry weight, and low during the summer months, 257.21 to 465.49 ng/g dry weight. The concentration of high molecular weight PAHs (HMWPAHs), consisting of 5–6 rings, was greater than that of low molecular weight PAHs (LMWPAHs), which had 2–3 rings. The total incremental lifetime cancer risk (ILCR) for both dermal and ingestion pathways was high for both adults and children during the four seasons, with the highest records as the following: winter > spring > summer > autumn. The ecological effects of the 16 PAHs were negligible except for acenaphthylene (Acy) and fluorene (Fl), which displayed slightly higher concentrations during the autumn and spring, respectively.

Performance evaluation of four sampling techniques and source apportionment for the atmospheric deposition fluxes of polycyclic aromatic hydrocarbons

Polycyclic aromatic hydrocarbons (PAHs) are primarily emitted into the atmosphere through anthropogenic activities and can be transported to receptor sites at varying distances. In this study, the atmospheric PAH deposition was investigated using a dry deposition plate (DDP) with Mylar, a dry deposition disk (DDD) with Velcro, a resin bulk deposition sampler (Resin-BDS), and a water bulk deposition sampler (Water-BDS) in Ulsan, South Korea, during May–October 2013. Additionally, ambient PAH concentrations were monitored using high-volume air samplers. The mean deposition fluxes of Σ13 PAHs were 8.62 ± 1.44, 36.9 ± 6.81, 56.9 ± 9.74, and 63.8 ± 8.04 μg/m2/d for the DDP, DDD, Resin-BDS, and Water-BDS, respectively. The DDD was more effective than the DDP because it could collect high molecular weight (HMW) PAHs from dry deposition, which are more toxic than low molecular weight PAHs. The Water-BDS had the highest fluxes of Σ13 PAHs; however, the Resin-BDS may be more suitable for collecting HMW PAHs from both dry and wet deposition due to relatively constant values for the deposition velocity of PAHs. Furthermore, the PAH fluxes in the Resin-BDS samples were significantly positively correlated with the gaseous and total (gaseous + particulate) concentrations of ambient PAHs. Hence, the fluxes obtained by the Resin-BDS were further used to apply principal component analysis, multiple linear regression, and backward air trajectory simultaneously to identify the emission sources of the deposited PAHs. The results indicate that the combustion of fossil fuels and biomass was the major source. In particular, the industrial complexes using petroleum and coal on the city's east coast and vehicular exhausts were the main local sources. Meanwhile, long-range sources may be forest fires, harbors, and industrial activities in nearby countries. Our study suggests that BDS, considering both dry and wet deposition, can be selectively used for research on PAH deposition.

Sources, gas-particle distribution and health risks of atmospheric PAHs in two typical basin cities in China

The sources of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere of various cities are highly intricate. Conducting research on the pollution characteristics of different types of PAHs in cities will help to focus on solving air pollution problems based on urban characteristics. Polycyclic aromatic hydrocarbons (PAHs) in the PM2.5-bound state and gas-phase were analyzed in the winter atmosphere of Yuncheng and Nanyang, China, to determine their pollution and spatial characteristics. The results revealed that in Yuncheng, the average concentrations of these 16 PAHs were 129.83 ± 96.63 ng m−3 in the PM2.5-bound form and 168.05 ± 88.64 ng m−3 in the gas phase, surpassing those observed in Nanyang, where the averages were 66.53 ± 32.49 ng m−3 and 112.80 ± 65.90 ng m−3 for particulate and gas phases, respectively. Gaseous samples primarily contained low molecular weight PAHs, while medium and high molecular weight PAHs were more prevalent in particulate samples. The linear relationship between the gas-particle partition coefficient (logKP) and the gas partition coefficient (PL0) and KOA value of PAHs in both cities suggested that during winter, PAHs in Yuncheng and Nanyang predominantly adsorb onto particles, failing to achieve gas-particle equilibrium. Source analysis using positive matrix factorization (PMF) identified coal combustion (26.4%–41.9%), biomass combustion (26.3%–29.6%), motor vehicle emissions (16.3%–30.4%), and evaporation sources (15.8%–26.9%) as the primary sources of atmospheric PAHs in both cities. Potential source contribution function (PSCF) and concentration-weighted trajectory (CWT) analyses indicated that pollutants originating from the northwest direction and near-earth air masses exerted a substantial influence on both cities. According to health risk assessments, both Yuncheng City and Nanyang City exhibited a certain risk of cancer due to atmospheric PAH exposure. However, the risk of cancer was higher in Yuncheng City compared to Nanyang City. The research results uncover the pollution characteristics and primary sources of polycyclic aromatic hydrocarbons (PAHs) in different types of urban air. It emphasizes the substantial contribution of local pollution sources to atmospheric PAHs and emphasizes the necessity of prioritizing control measures.

Novel insights into the synergetic degradation of pyrene by microbial communities from mangroves in China

Pyrene is a high molecular weight polycyclic aromatic hydrocarbon (HMW-PAHs). It is a ubiquitous, persistent, and carcinogenic environmental contaminant that has raised concern worldwide. This research explored synergistic bacterial communities for efficient pyrene degradation in seven typical Southern China mangroves. The bacterial communities of seven typical mangroves were enriched by pyrene, and enriched bacterial communities showed an excellent pyrene degradation capacity of > 95% (except for HK mangrove and ZJ mangrove). Devosia, Hyphomicrobium, Flavobacterium, Marinobacter, Algoriphahus, and Youhaiella all have significant positive correlations with pyrene (R>0, p < 0.05) by 16SrRNA gene sequencing and metagenomics analysis, indicated that these genera play a vital role in pyrene metabolism. Meanwhile, the functional genes were involved in pyrene degradation that was enriched in the bacterial communities, including the genes of nagAa, ndoR, pcaG, etc. Furthermore, the analyses of functional genes and binning genomes demonstrated that some bacterial communities as a unique teamwork to cooperatively participate in pyrene degradation. Interestingly, the genes related to biogeochemical cycles were enriched, such as narG , soxA, and cyxJ, suggested that bacterial communities were also helpful in maintaining the stability of the ecological environment. In addition, some novel species with pyrene-degradation potential were identified in the pyrene-degrading bacterial communities, which can enrich the resource pool of pyrene-degrading strains. Overall, this study will help develop further research strategies for pollutant removal.

A novel mycelial pellet applied to remove polycyclic aromatic hydrocarbons: High adsorption performance & its mechanisms

Mycelial pellets formed by Penicillium thomii ZJJ were applied as efficient biosorbents for the removal of polycyclic aromatic hydrocarbons (PAHs), which are a type of ubiquitous harmful hydrophobic pollutants. The live mycelial pellets were able to remove 93.48 % of pyrene at a concentration of 100 mg/L within 48 h, demonstrating a maximum adsorption capacity of 285.63 mg/g. Meanwhile, the heat-killed one also achieved a removal rate of 65.01 %. Among the six typical PAHs (pyrene, phenanthrene, fluorene, anthracene, fluoranthene, benzo[a]pyrene), the mycelial pellets preferentially adsorbed the high molecular weight PAHs, which also have higher toxicity, resulting in higher removal efficiency. The experimental results showed that the biosorption of mycelial pellets was mainly a spontaneous physical adsorption process that occurred as a monolayer on a homogeneous surface, with mass transfer being the key rate-limiting step. The main adsorption sites on the surface of mycelia were carboxyl and N-containing groups. Extracellular polymeric substances (EPS) produced by mycelial pellets could enhance adsorption, and its coupling with dead mycelia could achieve basically the same removal effect to that of living one. It can be concluded that biosorption by mycelial pellets occurred due to the influence of electrostatic and hydrophobic interactions, consisting of five steps. Furthermore, the potential applicability of mycelial pellets has been investigated considering diverse factors. The mycelia showed high environmental tolerance, which could effectively remove pyrene across a wide range of pH and salt concentration. And pellets diameters and humic acid concentration had a significant effect on microbial adsorption effect. Based on a cost-effectiveness analysis, mycelium pellets were found to be a low-cost adsorbent. The research outcomes facilitate a thorough comprehension of the adsorption process of pyrene by mycelial pellets and their relevant applications, proposing a cost-effective method without potential environmental issues (heat-killed mycelial pellets plus EPS) to removal PAHs.

Dermal absorption of high molecular weight parent and alkylated polycyclic aromatic hydrocarbons from manufactured gas plant soils using in vitro assessment

An enhanced in vitro human dermal bioavailability method was developed to measure the release of twenty parent and seven alkylated high molecular weight (HMW) polycyclic aromatic hydrocarbons (PAHs) from contaminated soils collected from five former manufactured Gas Plants (MGP) in England. GC-MS/MS was used to quantify HMW PAHs in soil, Strat-M artificial membrane representing skin, and synthetic receptor solution (RS) representing systemic circulation at 1-h, 10-h, and 24-h timesteps. Fluoranthene and pyrene exhibited the highest fluxes from soils to membrane (ranging from 9.5 - 281 ng/cm2/h) and soil to RS (<LOQ to 16.9 ng/cm2/h). Chrysene, benzo[a]anthracene, benzo[b]fluoranthene and the alkylated C1-fluoranthene/pyrene homologue series demonstrated fluxes higher than other HMW PAHs. The dermal fluxes were generally lower than those reported in previous investigations and suggests that dermal absorption varies between both HMW parent and alkylated PAHs and individual PAHs. The utilisation of real-world contaminated soils allowed for a more realistic representation; this is important because current risk assessment guidance is baseed on results from experiments that used artificially spiked soils. This research shows that the the ranges of dermal fluxes are PAH dependent and impact the mass of absorbed from soil after dermal exposure and therefore the potential risk contaminated soil poses to human health.

Formation and biotoxicity of environmentally persistent free radicals in steelworks soil under thermal treatment

Thermal treatment are commonly used to address organic contaminated soils. In particular, the pyrolysis of organic substances can result in the creation of environmentally persistent free radicals (EPFRs). We investigated a steelworks site in Chongqing (China) to observe changes in EPFRs before and after thermal treatment. Our findings revealed that the EPFRs were carbon-centered radicals with a g-factor < 2.0030 and a spin density ranging from n.d.–5.23 × 1015 spins/mg. The formation of EPFRs was driving by polycyclic aromatic hydrocarbons (PAHs), Mn, Cu, and total organic carbon (TOC). Following the thermal treatment, the spin densities of EPFRs increased by a factor of 0.25 to 1.81, with maximum levels reached at 300 °C. High molecular weight PAHs exhibited high heat capacity, enabling the generation of more EPFRs. The thermal decay of EPFRs occurred in two stages, with the shortest 1/e lifetime lasting up to 16.8 h. Raising the temperature or prolonging time can significantly reduce EPFRs levels. Thermal treatment increased the generation of EPFRs, hydroxyl radicals (•OH) and superoxide radical (•O2–), leading to a decrease in bacterial luminescence. Specifically, •OH contributed to approximately 73% of the B. brilliantus inhibition. Our results highlight that the thermal treatment significantly enhance EPFRs concentrations, and the treated soil remained ecologically risky. The knowledge of the formation of EPFRs and their biotoxicity is shedding new light on the thermal treatment risk management.

Biochars assisted phytoremediation of polycyclic aromatic hydrocarbons contaminated agricultural soil: Dynamic responses of functional genes and microbial community

A biochar-intensified phytoremediation experiment was designed to investigate the dynamic effects of different biochars on polycyclic aromatic hydrocarbon (PAH) removal in ryegrass rhizosphere contaminated soil. Maize and wheat straw biochar pyrolyzed at 300 °C and 500 °C were amended into PAH-contaminated soil, and then ryegrass (Lolium multiflorum L.) was planted for 90 days. Spearman's correlations among PAH removal, enzyme activity, abundance of PAH-ring hydroxylating dioxygenase (PAH-RHDα), and fungal and bacterial community structure were analyzed to elucidate the microbial degradation mechanisms during the combined remediation process. The results showed that 500 °C wheat straw biochar had higher surface area and more nutrients, and significantly accelerated the phytoremediation of PAHs (62.5 %), especially for high molecular weight PAH in contaminated soil. The activities of urease and dehydrogenase and the abundance of total and PAH-degrading bacteria, which improved with time by biochar and ryegrass, had a positive correlation with the removal rate of PAHs. Biochar enhanced the abundance of gram-negative (GN) PAH-RHDα genes. The GN PAH-degraders, Sphingomonas, bacteriap25, Haliangium, and Dongia may play vital roles in PAH degradation in biochar-amended rhizosphere soils. Principal coordinate analysis indicated that biochar led to significant differences in fungal community structures before 30 days, while the diversity of the bacterial community composition depended on planting ryegrass after 60 days. These findings imply that the structural reshaping of microbial communities results from incubation time and the selection of biochar and ryegrass in PAH-contaminated soils. Applying 500 °C wheat straw biochar could enhance the rhizoremediation of PAH-contaminated soil and benefit the soil microbial ecology.

Variations of the atmospheric polycyclic aromatic hydrocarbon concentrations, sources, and health risk and the direct medical costs of lung cancer around the Bohai Sea against a background of pollution prevention and control in China

Abstract. The Bohai Sea (BS) region, an area of China that is severely polluted with atmospheric polycyclic aromatic hydrocarbons (PAHs), has received wide attention in recent decades. To characterize the variations of the concentrations and sources of PAHs from June 2014 to May 2019, 15 PAH congeners (Σ15PAHs) were measured in atmospheric samples (N = 228) collected at 12 sites around the BS, and the health risk and direct medical costs associated with lung cancer caused by exposure to PAHs were also estimated. The annual daily average concentration of Σ15PAHs was 56.78 ± 4.75 ng m−3, which was dominated by low molecular weight PAHs (LMW-PAHs) containing three rings (58.7 ± 7.8 %). During the 5-year sampling period, the atmospheric Σ15PAHs concentration reduced by 17.5 % for the whole BS region, with an especially large drop of 51.7 % observed in the tightly controlled area of Tianjin (TJ), which was mainly due to a decrease in the concentration of high molecular weight PAHs (HMW-PAHs) containing five or six rings. Generally, the concentration of Σ15PAHs was highest in winter and lowest in summer, which can mainly be attributed to the change in LMW-PAH concentration. Based on the positive matrix factorization (PMF) model, PAHs in the BS region were mainly ascribed to coal combustion and biomass burning. The PAH contributions of coal combustion and motor vehicles showed different trends for the BS region (PAHs from coal combustion rose by 7.2 % and PAHs from motor vehicles fell by 22.4 %) and for TJ (PAHs from coal combustion fell by 12.6 % and PAHs from motor vehicles rose by 6.9 %). The incidence of lung cancer (ILCR) caused by exposure to atmospheric PAHs decreased by 74.1 % and 91.6 % from 2014 to 2018 in the BS region and in TJ, respectively. This was mainly due to the decrease in the concentration of highly toxic HMW-PAHs and was reflected in USD 10.7 million of savings in direct medical costs of lung cancer caused by exposure to PAHs, which represent a decrease of 46.1 % compared to the corresponding costs before air pollution prevention and control was implemented around the BS. There was an even higher reduction in medical costs of 54.5 % in TJ. Hence, this study proves that implementing pollution prevention and control not only effectively reduced the concentration of pollutants and the risks caused by them, but it also significantly reduced the medical costs of diseases caused by the corresponding exposure.

Assessment of particulate PAHs toxicity from alcohol-diesel blends fuelled high compression ratio CI engine

Transport and power generation applications will play an important role in current and next-generation compression ignition (CI) engines. Methanol, ethanol, and butanol have emerged as potential alternative fuels for internal combustion engines capable of reducing overall greenhouse gases (GHG) and pollutant emissions. This study deals with the morphological characterization of particulate matter (PM) and toxicity assessment of polycyclic aromatic hydrocarbons (PAHs) for methanol, ethanol and butanol blending with diesel, and provides new findings and results in the specific literature. It defines new limits of alcohol fractions in diesel blends for their applications in CI engines. For the experimental assessment, a single-cylinder CI engine was used with an increased compression ratio (CR) from 17.5 to 26. Alcohol fraction of 20% (v/v) in diesel reduced the PM emissions in the range of 29–38% than diesel. PM was further reduced, up to ∼50%, for higher ethanol and butanol fractions (∼50%), and the soot morphological characteristics exhibit smaller particle sizes (400–600 nm) than diesel (up to 2 μm). Moreover, 20% of alcohol fraction led to a 34–60% reduction in PAHs. The toxicity evaluation of the tested alcohol-diesel blend indicates that high molecular weight PAHs and nitro-PAHs are the main contributors to the overall toxicity. Benzo[a]pyrene and dibenzo-anthracene were the prominent PAHs. Increasing the alcohol blend ratio significantly reduced the toxicity potential, ranging from 20 to 67%.